EP0349940B1 - Phthalimidohexanperacid, process for preparing the same and use thereof - Google Patents

Phthalimidohexanperacid, process for preparing the same and use thereof Download PDF

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Publication number
EP0349940B1
EP0349940B1 EP89112062A EP89112062A EP0349940B1 EP 0349940 B1 EP0349940 B1 EP 0349940B1 EP 89112062 A EP89112062 A EP 89112062A EP 89112062 A EP89112062 A EP 89112062A EP 0349940 B1 EP0349940 B1 EP 0349940B1
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Prior art keywords
acid
bleaching
compound
pap
hydrogen peroxide
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German (de)
French (fr)
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EP0349940A1 (en
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Hanspeter Dr. Gethöffer
Gerd Dr. Reinhardt
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • C07D207/408—Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms
    • C07D207/412—Acyclic radicals containing more than six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
    • C07D211/86—Oxygen atoms
    • C07D211/88—Oxygen atoms attached in positions 2 and 6, e.g. glutarimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • Inorganic persalts have long been known as bleach additives in detergents. However, since they only achieve their optimal bleaching power at temperatures above 60 ° C unfold, a number of organic compounds are used to activate them described during the washing process with hydrogen peroxide under Release of a peroxycarboxylic acid, which already react at 40 - 60 ° C has a bleaching effect.
  • N-acyl compounds tetraacetylethylene diamine, tetraacetyl methylene diamine, Tetraacetylglycoluril
  • activated esters penentaacetylglucose, Acetoxibenzenesulfonate sodium, benzoyloxybenzenesulfonate sodium
  • peroxycarboxylic acids have recently been described as bleaching systems for detergents.
  • peroxycarboxylic acids such as dodecanedipercarboxylic acid (EP 127 782) and monoperoxiphthalic acid (EP 27 693), succinic acid (DE 34 38 529), perglutaric acid (DE 35 39 036) and sulfoperbenzoic acid (EP 124 969) are described.
  • the problem with these peroxycarboxylic acids is their low storage stability, which is only partially ensured by special physical or chemical stabilization.
  • the invention relates to ⁇ -phthalimidoperoxihexanoic acid of the formula
  • step -a- The manufacture of the Imidocarboxylic acid in step -a- can in a manner known per se by reaction phthalic anhydride with ⁇ -aminocaproic acid (see Houben-Weyl, Methods of Organic Chemistry, XI / 2, p. 17).
  • the imidocarboxylic acid can also be made from ⁇ -caprolactam in a particularly cost-effective manner getting produced.
  • the lactam with the anhydride in the presence of Water under pressure for 2 to 20 hours, preferably 5 to 10 hours at a temperature of 100 to 250 ° C, preferably 120 to 200 ° C, in an inert gas atmosphere in one suitable reaction vessel implemented.
  • the overpressure can be 1 to 30 bar, preferably 2 to 5 bar.
  • the conversion of the imidocarboxylic acid obtained in step -a- to Imidopercarboxylic acid is made by reaction with an oxidation mixture Hydrogen peroxide and a strong acid. Hydrogen peroxide comes as 30 to 95 percent, preferably 35 to 50 percent aqueous solution used.
  • suitable acidic catalysts are methanesulfonic acid or an acidic ion exchanger. Sulfuric acid is considered 50 to 96 percent, preferably 75 to 96 percent aqueous solution used.
  • Hydrogen peroxide is 1 to 20 times, preferably 1.5 to 4 times molar excess used. It has also proven to be beneficial Add hydrogen peroxide in portions. Generally a 2- to 5-fold excess of sulfuric acid - based on the imidocarboxylic acid - used.
  • the reaction temperature is between 5 and 50 ° C, preferably between 15 and 45 ° C.
  • the claimed imidoperoxy carboxylic acid precipitates out of the reaction mixture, can be easily isolated in step -c- by filtration or centrifugation will.
  • the precipitation process can be accelerated by adding water and to be completed. It is also possible by extraction with an organic Solvent to separate the imidoperoxy carboxylic acid.
  • the imidoperoxy carboxylic acid according to the invention is solid, almost odorless, has a low vapor pressure and is of excellent thermal stability. she can be used as a solution, powder or in processed form alone or in combination with other substances used for bleaching, oxidation or disinfection purposes will.
  • auxiliaries known per se such as boric acid, sulfates, Phosphates, carbonates, zeolites, carboxymethyl cellulose etc. and film-forming Substances such as fatty acids, fatty acid amides or esters, fatty alcohol polyglycol ethers or Polyethylene glycols possible.
  • the compound of the invention proves to be superior to that known bleaching system perborate / TAED (tetraacetylethylenediamine). While Perborate-based bleaching systems for blood stains to fixate the blood incline on the fabric and thereby drastically reduce its washability, this antagonistic effect becomes when using the described here Peroxycarboxylic acid according to the invention was not observed.
  • Compound in its bleaching efficiency on tea and red wine stains described peroxycarboxylic acids and dicarboxylic acids described peroxycarboxylic acids and dicarboxylic acids. It is advantageous significant oil solubility of the compound described here, thereby in particular hydrophobic oil-containing soiling such as grill oil or Spaghetti sauce to be bleached well.
  • the tests were carried out at 40 and 60 ° C in the Launder-O-Meter using the test stains tea on WFK cotton, red wine on EMPA cotton and standard soiling on WFK cotton.
  • the bleaching systems were metered in such a way that 25 mg / l of active oxygen resulted in the wash liquor. 1.5 g / l IEC detergent were used as detergents. The washing time was 30 minutes. The bleaching effect was determined as an increase in reflectance on the various test fabrics.
  • the evaluation is carried out in the usual way.
  • Bleaching system Remission values default tea red wine 40 ° C 60 ° C 40 ° C 60 ° C 40 ° C 60 ° C Perborate 49.5 59.4 58.4 62.8 55.5 56.9 Perborate / TAED 48.3 63.6 66.9 67.4 59.8 60.0 PAP 49.0 64.9 72.2 75.0 67.7 73.1
  • the tests were carried out in a Miele washing machine (Automatic W432) with the 40 ° temperature program (main wash and step spin) using 2 kg of fiber.
  • the bleaching effect was measured as an increase in reflectance on EMPA test strips (EMPA 103).
  • EMPA 103 EMPA test strips
  • 4.5 g / l of detergent were used, which were produced by mixing IEC detergent with the respective bleaching system.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Hydrogenated Pyridines (AREA)
  • Pyrrole Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Description

Anorganische Persalze sind seit langem als Bleichzusätze in Waschmitteln bekannt. Da sie ihre optimale Bleichkraft jedoch erst bei Temperaturen oberhalb 60°C entfalten, werden zu ihrer Aktivierung eine Reihe von organischen Verbindungen beschrieben, die während des Waschprozesses mit Wasserstoffperoxid unter Freisetzung einer Peroxicarbonsäure reagieren, welche bereits bei 40 - 60°C bleichend wirkt. Eine Übersicht zahlreicher bekannter Perborataktivatoren wie N-Acylverbindungen (Tetraacetylethylendiamin, Tetraacetylmethylendiamin, Tetraacetylglycoluril) oder aktivierte Ester (Pentaacetylglucose, Acetoxibenzolsulfonat-Natrium, Benzoyloxibenzolsulfonat-Natrium) ist z.B. in US 4, 248,928 gegeben.Inorganic persalts have long been known as bleach additives in detergents. However, since they only achieve their optimal bleaching power at temperatures above 60 ° C unfold, a number of organic compounds are used to activate them described during the washing process with hydrogen peroxide under Release of a peroxycarboxylic acid, which already react at 40 - 60 ° C has a bleaching effect. An overview of numerous well-known perborate activators such as N-acyl compounds (tetraacetylethylene diamine, tetraacetyl methylene diamine, Tetraacetylglycoluril) or activated esters (pentaacetylglucose, Acetoxibenzenesulfonate sodium, benzoyloxybenzenesulfonate sodium) is e.g. in U.S. 4,248,928.

Daneben werden in neuerer Zeit eine Reihe organischer Peroxicarbonsäuren als Bleichsysteme für Waschmittel beschrieben. Neben bereits kommerziell erhältlichen Peroxicarbonsäuren wie Dodecandipercarbonsäure (EP 127 782) und Monoperoxiphthalsäure (EP 27 693) sind Perbernsteinsäure (DE 34 38 529), Perglutarsäure (DE 35 39 036) und Sulfoperbenzoesäure (EP 124 969) beschrieben. Problematisch an diesen Peroxicarbonsäuren ist jedoch ihre geringe Lagerstabilität, die zum Teil erst durch besondere physikalische oder chemische Stabilisierung gewährleistet wird. Insbesondere hat sich hier die Herstellung von Magnesium-Salzen (EP 105 689) oder ein Zusatz von Phosphanoxid/Natriumsulfat (DE 33 20 497) bewährt. Nach EP 170 386 werden organische Peroxicarbonsäuren auch durch eine zusätzliche Amidgruppe im Molekül stabilisiert. Beispiele dafür sind N-Decanoyl-6-aminoperoxicapronsäure oder 3-(N-Nonyl-carbamoyl)perpropionsäure. Die Lagerstabilisät dieser Verbindungen kann durch Überführung in das Magnesiumsalz und durch Zugabe von Boraten zusätzlich gesteigert werden (US 4,686,063). Die bisher beschriebenen freien Peroxicarbonsäuren zeigen jedoch bereits unter relativ milden Lagerbedingungen eine deutliche Abnahme des Aktivsauerstoffs. Dies ist auch, wie eigene Versuche zeigen, bei den bereits in J. Chem. Soc. 1982, 3821 und Chem. Ind. 1961, 469 beschriebenen Imidopercarbonsäuren der Fall. Es besteht daher weiterhin ein großes Interesse an lagerstabilen organischen Peroxicarbonsäuren mit hoher Bleicheffizienz, die auf einfachem und sicherem Wege bequem zugänglich sind.In addition, a number of organic peroxycarboxylic acids have recently been described as bleaching systems for detergents. In addition to commercially available peroxycarboxylic acids such as dodecanedipercarboxylic acid (EP 127 782) and monoperoxiphthalic acid (EP 27 693), succinic acid (DE 34 38 529), perglutaric acid (DE 35 39 036) and sulfoperbenzoic acid (EP 124 969) are described. However, the problem with these peroxycarboxylic acids is their low storage stability, which is only partially ensured by special physical or chemical stabilization. In particular, the production of magnesium salts (EP 105 689) or the addition of phosphine oxide / sodium sulfate (DE 33 20 497) has proven successful. According to EP 170 386, organic peroxycarboxylic acids are also stabilized by an additional amide group in the molecule. Examples include N-decanoyl-6-aminoperoxicaproic acid or 3- (N-nonyl-carbamoyl) perpropionic acid. The storage stability of these compounds can be increased further by conversion into the magnesium salt and by adding borates (US Pat. No. 4,686,063). However, the free peroxycarboxylic acids described so far show a clear decrease in active oxygen even under relatively mild storage conditions. This is also, as our own experiments show, in the case of J. Chem. Soc. 1982 , 3821 and Chem. Ind. 1961 , 469 the imidopercarboxylic acids described. There is therefore still great interest in storage-stable organic peroxycarboxylic acids with high bleaching efficiency which are easily and safely accessible.

Gegenstand der Erfindung ist ω-Phthalimidoperoxihexansäure der Formel

Figure 00020001
The invention relates to ω-phthalimidoperoxihexanoic acid of the formula
Figure 00020001

Die Herstellung dieser Verbindung erfolgt durch die Schritte:

  • -a- Synthese der Imidocarbonsäure
  • -b- Oxidation zur Percarbonsäure
  • -c- Isolierung der Imidoperoxicarbonsäure.
    • This connection is established through the following steps:
  • -a- Synthesis of imidocarboxylic acid
  • -b- Oxidation to percarboxylic acid
  • -c- Isolation of imidoperoxy carboxylic acid.

    • Im folgenden werden die einzelnen Schritte näher erläutert. Die Herstellung der Imidocarbonsäure im Schritt -a- kann in an sich bekannter Weise durch Umsetzung von Phthalsäureanhydrid mit ω-Aminocapronsäure erfolgen (s. Houben-Weyl, Methoden der Organischen Chemie, XI/2, S. 17).The individual steps are explained in more detail below. The manufacture of the Imidocarboxylic acid in step -a- can in a manner known per se by reaction phthalic anhydride with ω-aminocaproic acid (see Houben-Weyl, Methods of Organic Chemistry, XI / 2, p. 17).

    Die Imidocarbonsäure kann besonders kostengünstig auch aus ε-Caprolactam hergestellt werden. Hierzu wird das Lactam mit dem Anhydrid in Gegenwart von Wasser unter Druck 2 bis 20 h, vorzugsweise 5 bis 10 h bei einer Temperatur von 100 bis 250°C, vorzugsweise 120 bis 200°C, unter Inertgasatmosphäre in einem geeigneten Reaktionsgefäß umgesetzt. Der Überdruck kann 1 bis 30 bar, vorzugsweise 2 bis 5 bar betragen.The imidocarboxylic acid can also be made from ε-caprolactam in a particularly cost-effective manner getting produced. For this, the lactam with the anhydride in the presence of Water under pressure for 2 to 20 hours, preferably 5 to 10 hours at a temperature of 100 to 250 ° C, preferably 120 to 200 ° C, in an inert gas atmosphere in one suitable reaction vessel implemented. The overpressure can be 1 to 30 bar, preferably 2 to 5 bar.

    Die Umwandlung der im Schritt -a- erhaltenen Imidocarbonsäure zur Imidopercarbonsäure erfolgt durch Umsetzung mit einem Oxidationsgemisch aus Wasserstoffperoxid und einer starken Säure. Wasserstoffperoxid kommt als 30 bis 95 prozentige, vorzugsweise 35 bis 50 prozentige wäßrige Lösung zum Einsatz. Geeignete saure Katalysatoren sind neben Schwefelsäure Methansulfonsäure oder ein saurer Ionenaustauscher. Schwefelsäure wird als 50 bis 96 prozentige, vorzugsweise 75 bis 96 prozentige wäßrige Lösung verwendet.The conversion of the imidocarboxylic acid obtained in step -a- to Imidopercarboxylic acid is made by reaction with an oxidation mixture Hydrogen peroxide and a strong acid. Hydrogen peroxide comes as 30 to 95 percent, preferably 35 to 50 percent aqueous solution used. In addition to sulfuric acid, suitable acidic catalysts are methanesulfonic acid or an acidic ion exchanger. Sulfuric acid is considered 50 to 96 percent, preferably 75 to 96 percent aqueous solution used.

    Wasserstoffperoxid wird in 1- bis 20-fachem, vorzugsweise 1.5- bis 4-fachem molarem Überschuß verwendet. Es hat sich ferner als günstig erwiesen, die Wasserstoffperoxidzugabe portionsweise vorzunehmen. Im allgemeinen wird ein 2- bis 5-facher Überschuß an Schwefelsäure - bezogen auf die Imidocarbonsäure - eingesetzt. Die Reaktionstemperatur liegt zwischen 5 und 50°C, vorzugsweise zwischen 15 und 45°C.Hydrogen peroxide is 1 to 20 times, preferably 1.5 to 4 times molar excess used. It has also proven to be beneficial Add hydrogen peroxide in portions. Generally a 2- to 5-fold excess of sulfuric acid - based on the imidocarboxylic acid - used. The reaction temperature is between 5 and 50 ° C, preferably between 15 and 45 ° C.

    Da die beanspruchte Imidoperoxicarbonsäure aus dem Reaktionsgemisch ausfällt, kann sie in Schritt -c- in einfacher Weise durch Filtration oder Zentrifugation isoliert werden. Der Ausfällungsprozess kann durch Zugaben von Wasser beschleunigt und vervollständigt werden. Es ist auch möglich, durch Extraktion mit einem organischen Lösemittel die Imidoperoxicarbonsäure abzutrennen.Since the claimed imidoperoxy carboxylic acid precipitates out of the reaction mixture, can be easily isolated in step -c- by filtration or centrifugation will. The precipitation process can be accelerated by adding water and to be completed. It is also possible by extraction with an organic Solvent to separate the imidoperoxy carboxylic acid.

    Die erfindungsgemäße Imidoperoxicarbonsäure ist fest, nahezu geruchlos, besitzt einen niedrigen Dampfdruck und ist von ausgezeichneter thermischer Stabilität. Sie kann als Lösung, Pulver oder in verarbeiteter Form allein oder in Kombination mit weiteren Stoffen zu Bleich-, Oxidations- oder Desinfektionszwecken eingesetzt werden.The imidoperoxy carboxylic acid according to the invention is solid, almost odorless, has a low vapor pressure and is of excellent thermal stability. she can be used as a solution, powder or in processed form alone or in combination with other substances used for bleaching, oxidation or disinfection purposes will.

    Bevorzugt wird sie als Bleichmittel in festen oder flüssigen Wasch- und Reinigungsmitteln eingesetzt, da ihre bleichende und desinfizierende Wirkung bereits in einem weiten Temperaturbereich unterhalb von 60°C voll wirksam wird. It is preferred as a bleach in solid or liquid detergents Detergents used because of their bleaching and disinfecting effects becomes fully effective in a wide temperature range below 60 ° C.

    Zur Einarbeitung in pulverförmige Waschmittel eignet sie sich insbesondere in granulierter, extrudierter, tablettierter oder agglomerierter Form. Als Zusätze bei dieser Verarbeitungsweise sind an sich bekannte Hilfsmittel wie Borsäure, Sulfate, Phosphate, Carbonate, Zeolithe, Carboximethylcellulose usw. und filmbildende Stoffe wie Fettsäuren, Fettsäureamide oder -ester, Fettalkoholpolyglykolether oder Polyethylenglykole möglich.It is particularly suitable for incorporation into powder detergents in granulated, extruded, tableted or agglomerated form. As additives at This method of processing includes auxiliaries known per se, such as boric acid, sulfates, Phosphates, carbonates, zeolites, carboxymethyl cellulose etc. and film-forming Substances such as fatty acids, fatty acid amides or esters, fatty alcohol polyglycol ethers or Polyethylene glycols possible.

    Die erfindungsgemäße Verbindung erweist sich als überlegen im Vergleich zu dem bekannten Bleichsystem Perborat/TAED (Tetraacetylethylendiamin). Während Bleichsysteme auf Perborat-Basis bei Blutanschmutzungen zur Fixierung des Blutes auf dem Gewebe neigen und damit seine Auswaschbarkeit drastisch herabsetzen, wird dieser antagonistische Effekt beim Einsatz der hier beschriebenen erfindungsgemäßen Peroxicarbonsäure nicht beobachtet.The compound of the invention proves to be superior to that known bleaching system perborate / TAED (tetraacetylethylenediamine). While Perborate-based bleaching systems for blood stains to fixate the blood incline on the fabric and thereby drastically reduce its washability, this antagonistic effect becomes when using the described here Peroxycarboxylic acid according to the invention was not observed.

    Bei Verwendung äquimolarer Mengen an Aktivsauerstoff ist die erfindungsgemäße Verbindung in ihrer Bleicheffizient an Tee- und Rotweinanschmutzungen den bisher beschriebenen Peroxicarbonsäuren und -dicarbonsäuren überlegen. Vorteilhaft ist weiterhin eine signifikante Öllöslichkeit der hier beschrieben Verbindung, wodurch insbesondere hydrophobe ölhaltige Anschmutzungen wie Grillöl oder Spaghettisauce gut gebleicht werden.When using equimolar amounts of active oxygen, this is the invention Compound in its bleaching efficiency on tea and red wine stains described peroxycarboxylic acids and dicarboxylic acids. It is advantageous significant oil solubility of the compound described here, thereby in particular hydrophobic oil-containing soiling such as grill oil or Spaghetti sauce to be bleached well.

    Beispielexample a) ω-Phthalimidohexansäurea) ω-phthalimidohexanoic acid

    113,2 g (1 Mol) ε-Caprolactam, 18 g Wasser und 148,1 g (1 Mol) Phthalsäureanhydrid werden in einem Autoklaven 5 h bei 160°C und 3 bar Stickstoff zur Reaktion gebracht. Die Schmelze wird anschließend in eine Porzellanschale gegossen.

  • Ausbeute: 261 g (99,8 %), weiße Kristalle
  • Fp: 104 - 105°C
    • 113.2 g (1 mol) of ε-caprolactam, 18 g of water and 148.1 g (1 mol) of phthalic anhydride are reacted in an autoclave for 5 hours at 160 ° C. and 3 bar nitrogen. The melt is then poured into a porcelain bowl.
  • Yield: 261 g (99.8%), white crystals
  • Mp: 104-105 ° C

    • b) ω-Phthalimidoperoxihexansäureb) ω-phthalimidoperoxyhexanoic acid

    653,2 g (2,5 Mol) ω-Phthalimidohexansäure werden wie folgt oxidiert:653.2 g (2.5 mol) of ω-phthalimidohexanoic acid are oxidized as follows:

    Die Imidocarbonsäure wird in der 2- is 2,5-fachen Menge Schwefelsäure gelöst und tropfenweise mit 2,5 Äquivalenten Wasserstoffperoxid (35 - 50 prozentig) unter Eiskühlung 50 versetzt, daß die Innentemperatur zwischen 40 und 45°C gehalten werden kann. Nach erfolgter Zugabe wird auf 25 - 30°C gekühlt, mit Wasser verdünnt und die ausgefallene Persäure abgesaugt. Der Filterkuchen wird mit Wasser gewaschen und im Vakuumtrockenschrank bei 35°C getrocknet.

  • Ausbeute: 636,6 g (91,8 %), weiße Kristalle
  • Aktivsauerstoffgehalt: 5,4 % (93,6 %)
  • Fp: 89 - 90°C
    • The imidocarboxylic acid is dissolved in 2 to 2.5 times the amount of sulfuric acid and 2.5 equivalents of hydrogen peroxide (35-50 percent) are added dropwise with ice cooling 50 so that the internal temperature can be kept between 40 and 45 ° C. After the addition, the mixture is cooled to 25-30 ° C., diluted with water and the precipitated peracid is suctioned off. The filter cake is washed with water and dried in a vacuum drying cabinet at 35 ° C.
  • Yield: 636.6 g (91.8%), white crystals
  • Active oxygen content: 5.4% (93.6%)
  • Mp: 89-90 ° C

    • Waschversuche im Launder-O-MeterWashing attempts in the Launder-O-Meter

    Die Versuche wurden bei 40 und 60°C im Launder-O-Meter unter Verwendung der Testanschmutzungen Tee auf WFK-Baumwolle, Rotwein auf EMPA-Baumwolle und Standard-Anschmutzung auf WFK-Baumwolle durchgeführt. Die Bleichsysteme wurden so dosiert, daß jeweils 25 mg/l Aktivsauerstoff in der Waschflotte resultierten. Als Waschmittel wurden jeweils 1,5 g/l IEC-Waschmittel eingesetzt. Die Waschzeit betrug 30 min. Die Bleichwirkung wurde als Remissionszunahme an den verschiedenen Testgeweben bestimmt. Die Auswertung erfolgt in gewohnter Weise. Bleichsystem Remissionswerte Standard Tee Rotwein 40°C 60°C 40°C 60°C 40°C 60°C Perborat 49,5 59,4 58,4 62,8 55,5 56,9 Perborat/TAED 48,3 63,6 66,9 67,4 59,8 60,0 PAP 49,0 64,9 72,2 75,0 67,7 73,1 The tests were carried out at 40 and 60 ° C in the Launder-O-Meter using the test stains tea on WFK cotton, red wine on EMPA cotton and standard soiling on WFK cotton. The bleaching systems were metered in such a way that 25 mg / l of active oxygen resulted in the wash liquor. 1.5 g / l IEC detergent were used as detergents. The washing time was 30 minutes. The bleaching effect was determined as an increase in reflectance on the various test fabrics. The evaluation is carried out in the usual way. Bleaching system Remission values default tea red wine 40 ° C 60 ° C 40 ° C 60 ° C 40 ° C 60 ° C Perborate 49.5 59.4 58.4 62.8 55.5 56.9 Perborate / TAED 48.3 63.6 66.9 67.4 59.8 60.0 PAP 49.0 64.9 72.2 75.0 67.7 73.1

    Die Ergebnisse zeigen bei äquimolarem Einsatz der Bleichsysteme eine deutlich bessere Bleichleistung der erfindungsgemäßen Persäure PAP (ω-Phthalimidoperoxihexansäure) gegenüber dem bisher üblichen Bleichsystem Perborat/TAED (Tetraacetylethylendiamin).The results show a clear when equimolar use of the bleaching systems better bleaching performance of the peracid PAP according to the invention (ω-phthalimidoperoxihexanoic acid) compared to the previously usual bleaching system Perborate / TAED (tetraacetylethylene diamine).

    Waschversuche im Launder-O-MeterWashing attempts in the Launder-O-Meter

    Die Versuche wurden analog wie zuvor beschrieben durchgeführt. Als Bleichsysteme wurden die Peroxicarbonsäuren DPDDA (Diperoxidodecandisäure), PMP (Monoperphthalsäure), NAPSA (Nonylmonoamidoperbernsteinsäure) gegen PAP ausgeprüft. Peroxisäuren Remissionswerte Tee Rotwein 38°C 60°C 38°C 60°C DPDDA 69,6 73,6 65,5 71,8 PMP 66,8 71,1 61,1 65,4 NAPSA 68,1 72,2 63,7 68,6 PAP 68,4 77,1 67,2 74,3 The tests were carried out analogously to that described above. The peroxycarboxylic acids DPDDA (diperoxidodecanedioic acid), PMP (monoperphthalic acid) and NAPSA (nonylmonoamido succinic acid) were tested against PAP as bleaching systems. Peroxyacids Remission values tea red wine 38 ° C 60 ° C 38 ° C 60 ° C DPDDA 69.6 73.6 65.5 71.8 PMP 66.8 71.1 61.1 65.4 NAPSA 68.1 72.2 63.7 68.6 PAP 68.4 77.1 67.2 74.3

    Waschversuche in der WaschmaschineAttempted washing in the washing machine

    Die Versuche wurden in einer Miele Waschmaschine (Automatic W432) mit dem 40°-Temperaturprogramm (Hauptwäsche und Stufenschleudern) unter Verwendung von 2 kg Ballaststoff durchgeführt. Die Bleichwirkung wurde als Remissionszunahme an EMPA-Teststreifen (EMPA 103) gemessen. Es wurden jeweils 4,5 g/l Waschmittel eingesetzt, die durch Mischen von IEC-Waschmittel mit dem jeweiligen Bleichsystem hergestellt wurden. Waschmittel Standard Rotwein Blut IEC 24,7 54,8 65,5 IEC/10 % Perborat 27,8 54,9 37,1 IEC/10 % Perborat/3 % TAED 28,0 57,7 44,2 IEC/3 % PAP 32,2 57,8 68,5 IEC/6 % PAP 34,9 63,1 66,6 IEC/9 % PAP 34,4 66,6 65,5 IEC/6 % DSIPH 36,6 59,1 65,6 TAED = Tetraacetylethylendiamin
    PAP = ω-Phthalimidoperoxihexansäure
    DSIPH = ω-[2-Dodecylsuccinimido]-peroxihexansäure         The tests were carried out in a Miele washing machine (Automatic W432) with the 40 ° temperature program (main wash and step spin) using 2 kg of fiber. The bleaching effect was measured as an increase in reflectance on EMPA test strips (EMPA 103). In each case 4.5 g / l of detergent were used, which were produced by mixing IEC detergent with the respective bleaching system. laundry detergent default red wine blood IEC 24.7 54.8 65.5 IEC / 10% perborate 27.8 54.9 37.1 IEC / 10% perborate / 3% TAED 28.0 57.7 44.2 IEC / 3% PAP 32.2 57.8 68.5 IEC / 6% PAP 34.9 63.1 66.6 IEC / 9% PAP 34.4 66.6 65.5 IEC / 6% DSIPH 36.6 59.1 65.6 TAED = tetraacetylethylenediamine
    PAP = ω-phthalimidoperoxyhexanoic acid
    DSIPH = ω- [2-dodecylsuccinimido] peroxyhexanoic acid

    Die Versuche zeigen eine deutliche Überlegenheit der erfindungsgemäßen Imidoperoxicarbonsäure gegenüber bekannten Bleichsystemen. Insbesondere wird bei Verwendung dieser Persäuren kein antagonistischer Effekt bei der Auswaschbarkeit von Blutflecken beobachtet. The tests show a clear superiority of the invention Imidoperoxy carboxylic acid compared to known bleaching systems. In particular no antagonistic effect in the use of these peracids Washability of blood stains observed.

    Beispiel 14Example 14 Bestimmung der Öllöslichkeit von BleichsystemenDetermination of the oil solubility of bleaching systems

    Zur Bestimmung der Öllöslichkeit eines Bleichsystems wurde das Bleichsystem bei 20°C in eine Mischung aus 50 % E-Wasser und 50 % Isopropylmyristat eingetragen, der pH-Wert auf 9 eingestellt und das Gemisch 10 min intensiv verrührt. Nach der Phasentrennung wurde der Peroxicarbonsäureanteil in Öl- und Wasserphase titrimetrisch bestimmt. Bleichsystem Öllöslichkeit bei pH 9 Perborat/TAED 6 % DPDDA 15 % PAP 38 % Perborat/Isonobs 54 % DSIPH 86 % To determine the oil solubility of a bleaching system, the bleaching system was introduced at 20 ° C. into a mixture of 50% deionized water and 50% isopropyl myristate, the pH was adjusted to 9 and the mixture was stirred intensively for 10 minutes. After phase separation, the proportion of peroxycarboxylic acid in the oil and water phases was determined by titration. Bleaching system Oil solubility at pH 9 Perborate / TAED 6% DPDDA 15% PAP 38% Perborate / Isonobs 54% DSIPH 86%

    Lagerversuche der freien PeroxicarbonsäurenStorage tests of free peroxycarboxylic acids

    Die Versuche wurden in offenen Gefäßen im Wärmeschrank durchgeführt. Der Gehalt an Peroxicarbonsäure wurde titrimetrisch bestimmt. Peroxicarbonsäure Lagerzeit (Wochen) Temperatur Aktivsauerstoffverlust PAP 4 25°C 1,4 % NAPSA 4 25°C 14,6 % PAP 4 40°C 2,0 % NAPSA 4 40°C 29,3 % PAP 4 50°C 12,0 % NAPSA 2 50°C 100,0 % The tests were carried out in open vessels in the warming cabinet. The content of peroxycarboxylic acid was determined titrimetrically. Peroxycarboxylic acid Storage time (weeks) temperature Active oxygen loss PAP 4th 25 ° C 1.4% NAPSA 4th 25 ° C 14.6% PAP 4th 40 ° C 2.0% NAPSA 4th 40 ° C 29.3% PAP 4th 50 ° C 12.0% NAPSA 2nd 50 ° C 100.0%

    Claims (6)

    1. A compound of the formula
      Figure 00100001
    2. A process for the preparation of the compound as claimed in claim 1, which comprises reacting phthalic anhydride with ω-aminocaproic acid and oxidizing the resulting imidocarboxylic acid using hydrogen peroxide in the presence of a strong acid.
    3. A process for the preparation of the compound as claimed in claim 1, which comprises reacting phthalic anhydride with caprolactam under pressure in the presence of water and oxidizing the resulting imidocarboxylic acid using hydrogen peroxide in the presence of a strong acid.
    4. The process as claimed in claim 3, wherein the reaction is carried out at a gage pressure of from 1 to 30 bar, preferably from 2 to 5 bar.
    5. The process as claimed in claim 3 or 4, wherein the reaction is carried out over a period of from 2 to 20 h, preferably from 5 to 10 h, at a temperature of from 100 to 250°C, preferably from 120 to 200°C, under an inert gas atmosphere.
    6. The use of the compound as claimed in claim 1 in bleaching, oxidizing and cleaning compositions.
    EP89112062A 1988-07-08 1989-07-01 Phthalimidohexanperacid, process for preparing the same and use thereof Expired - Lifetime EP0349940B1 (en)

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    US7179778B2 (en) 2002-12-06 2007-02-20 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Liquid acid detergent comprising a phthaloylamino peroxy caproic acid
    US7183247B2 (en) 2002-12-17 2007-02-27 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Method for the production of suspensions comprising phthalimidoperoxyhexanoic acid
    US8093198B2 (en) 2007-01-22 2012-01-10 Henkel Ag & Co. Kgaa Method for the production of particulate bleaching agent compositions
    WO2013178290A1 (en) 2012-06-01 2013-12-05 Ecolab Usa Inc. Stabilization of phthalimido percarboxylic acids with disaccharides
    WO2013178289A1 (en) 2012-06-01 2013-12-05 Ecolab Usa Inc. Stabilization of phthalimido percarboxylic with lithium salts
    WO2014183795A1 (en) 2013-05-17 2014-11-20 Ecolab Usa Inc. Stabilization of phthalimido percarboxylic acids with aminoalkanesulfonic acids

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    ZA895178B (en) 1990-03-28
    EP0349940A1 (en) 1990-01-10
    DE3823172C2 (en) 1998-01-22
    NO175204C (en) 1994-09-14
    CA1340443C (en) 1999-03-16
    DE58909834D1 (en) 1998-06-18
    US5994284A (en) 1999-11-30
    JPH0276850A (en) 1990-03-16
    NO892834D0 (en) 1989-07-07
    AR246265A1 (en) 1994-07-29
    AU3793489A (en) 1990-01-11
    US5061807A (en) 1991-10-29
    NO892834L (en) 1990-01-09
    ES2118055T3 (en) 1998-09-16
    NO175204B (en) 1994-06-06
    KR900001652A (en) 1990-02-27
    BR8903368A (en) 1990-02-13
    MX16730A (en) 1994-05-31
    JP3065322B2 (en) 2000-07-17
    DE3823172A1 (en) 1990-01-11
    AU624392B2 (en) 1992-06-11
    HK1009646A1 (en) 1999-06-04
    KR0135527B1 (en) 1998-04-23
    ATE166049T1 (en) 1998-05-15

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